Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
  • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
  • B65D25/00—Details of other kinds or types of rigid or semi-rigid containers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
  • B01J20/26—Synthetic macromolecular compounds
  • B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
  • B29C49/0005—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor characterised by the material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
  • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
  • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
  • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
  • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
  • B65D51/00—Closures not otherwise provided for
  • B65D51/24—Closures not otherwise provided for combined or co-operating with auxiliary devices for non-closing purposes
  • B65D51/244—Closures not otherwise provided for combined or co-operating with auxiliary devices for non-closing purposes provided with oxygen absorbers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
  • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
  • B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
  • B65D81/24—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants
  • B65D81/26—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants with provision for draining away, or absorbing, or removing by ventilation, fluids, e.g. exuded by contents; Applications of corrosion inhibitors or desiccators
  • B65D81/266—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants with provision for draining away, or absorbing, or removing by ventilation, fluids, e.g. exuded by contents; Applications of corrosion inhibitors or desiccators for absorbing gases, e.g. oxygen absorbers or desiccants
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
  • C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
  • C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/6858—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/91—Polymers modified by chemical after-treatment
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K11/00—Use of ingredients of unknown constitution, e.g. undefined reaction products
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/01—Hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
  • C08K5/098—Metal salts of carboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/10—Esters; Ether-esters
  • C08K5/101—Esters; Ether-esters of monocarboxylic acids
  • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/20—Carboxylic acid amides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
  • C08K5/3445—Five-membered rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/41—Compounds containing sulfur bound to oxygen
  • C08K5/42—Sulfonic acids; Derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
  • C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C2949/00—Indexing scheme relating to blow-moulding
  • B29C2949/07—Preforms or parisons characterised by their configuration
  • B29C2949/0715—Preforms or parisons characterised by their configuration the preform having one end closed
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
  • B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
  • B29C49/06—Injection blow-moulding
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
  • B29K2067/003—PET, i.e. poylethylene terephthalate
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
  • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
  • B29K2105/0014—Catalysts
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
  • B29K2995/0037—Other properties
  • B29K2995/005—Oriented
  • B29K2995/0053—Oriented bi-axially
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
  • B29L2031/00—Other particular articles
  • B29L2031/712—Containers; Packaging elements or accessories, Packages
  • B29L2031/7158—Bottles
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
  • C08K2003/2237—Oxides; Hydroxides of metals of titanium
  • C08K2003/2241—Titanium dioxide
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K2201/00—Specific properties of additives
  • C08K2201/012—Additives improving oxygen scavenging properties
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2201/00—Properties
  • C08L2201/08—Stabilised against heat, light or radiation or oxydation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2203/00—Applications
  • C08L2203/10—Applications used for bottles
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2203/00—Applications
  • C08L2203/16—Applications used for films

Definitions

• United States Patent No. 7, 1 ⁇ ,159 B2 to Liu et ah 'Liu discloses a composition of a polyester, a partially aromatic ptxlyamide, a cobalt salt and an ionic compatibilizer that is a eopoiyester containing a metal sulfonate salt
• Liu teaches that the use of a transition metal catalyst to promote oxygen scavenging in polyamide cors.tai.ners is well known.
• Liu mtther teaches that blends of an ionic compatlbilixer (eopoiyester containing a metal sulfonate salt) and. a cobalt salt results in a container having improved gas barrier properties, improved haze and reduced yellowness.
• Liu also teaches that blends of polyesters and po!yamides suffer from issues of haze and yellowness.
• United States Patent No. 8,871,846 B2 to Eava discloses a composition of a polyester, a polyamjde, a transition metal catalyst and an inert organic compound selected from the group consisting of paraffins, vegetable oils, poiyaSkylene glycols* esters of polyols, aSkoxylates, and mixtures of these substances with linseed oils being an example of such a vegetable oil.
• Fava discloses that the use of an inert organic compound, which, preferably is liquid at ambient temperature* in transition metal-based poSyester/polyamide compositions for the forming of articles, e.g.
• a preform having a preform wall which may comprise a composition comprising at least one polyester component, a transition metal catalyst, and a vegetable oil comprising at least one moleenle having a double allyi.ic structure, wherein the at least one polyester component may comprise at least one acid unit and at least one dio! unit, the concentration of the double a!lylie structures of the vegetable oil in the composition may be greater than 5.0 meq/kg of all of the polyester components, and the preform may have an to value of less than 260 in an equation :
• L * is a Hunter L ' measurement in the range of between 0 and 100 excluding 0 and t is the tMekoess of the preform wall in mm.
• the at least one polyester component ma be a copotyester containing a metal sulfonate salt group
• the metal sulfonate salt group may be a metal sidfoisophthaiate derived from a metal salt ' of 5-sdfbisophihaUe acid, its dimethyl ester or its glycol ester.
• the metal salt of S-sulibisophthalic acid Its dimethyl ester or its glycol ester may further comprise a metal Ion selected from the group consisting of Na U ⁇ FT " , 3 ⁇ 4f : , Mn *' ⁇ Co ⁇ ' and Ca : .
• the metal sulfonate salt group is preferably present in. a range selected from the grou consisting of 0.01 to ⁇ 0.0.mole percent, 0.01 to 2.0 mole percent, 0.05 to 1.1 mole percent, 0.10 to 0.74 mole percent and OJO to 0 * 6 mole percent based upon the total mo!es of acid units in all of the polyester components.
• the transition metal catalyst may be a compound containing at least one cobalt atom in a positive valence state. It is further disclosed that the transition metal catalyst is preferably a salt containing at least one cobalt atom in a positive oxidation state. It is further disclosed that the transition metal catalyst is preferably added to the composition at a level in a range selected from the group of between 10 and 600 ppm, between 20 and 400 pprn and between 40 and 200 ppm of metal relative to the total amount of the polyester components and vegetable oil present in the composition.
• the vegetable oil may be selected from the group consisting of flax seed oil, linseed oil, evening primrose oil, borage oil, sunflower oil, soybean oil, grapeseed oil, corn oil, cotton seed oil., rice bran oil, oanola oil and peanut oil. It is further disclosed that the composition may have a concentration of the double ally tic structures of the vegetable oil in the composition greater than 7.0 meq kg of ail of the polyester components * It Is further disclosed that t he composition may have a concentration of the double allylie structures of the vegetable oil in the composition greater than. 9.0 meq/kg of all of the polyester components. It is further disclosed thai the composition may have a concentration of the double a!!yiic structures of the vegetable oil in the composi tion greater than 14.0 me /kg of all of the polyester components.
• the composition may further comprise a poSyamide.
• the preferred potyamide is poiy-metaxyiylene adiparnide, it is further disclosed thai the polyamide may be present in the composition at a level in a range selected from the group consisting of between 0.1 and 0.9 % by weight of the total composition, 0.1 to 0.8 % by weight of the total composition, 0 * 1 to 0 * 7 3 ⁇ 4 by weight of the total composition and 0,1 to 0,6 % by weight of the total composition.
• a blaxially oriented container manufactured from a preform.
• a preform having a preform wall which may comprise a composition comprising at least one polyester component, a transition metal catalyst, and a vegetable oil C'YQ" comprisin at least one molecule having a doable allylic structure, wherein the at least one polyester component may comprise at least one acid unit and at least one d.iol unit, the concentration of the double a!lylic structures of the vegetable oil in the com position may be greater than 5,0 nieq/kg of all of the polyester components, and the preform may have an ⁇ value of less than 50 in an equation: y— .... w .w;V...O. «
• L is a Hunter L ' measurement in the range of between 0 and .100 excluding 0 »
• i is the thickness of the preform wall, i mm, and the composition comprises a vegetable oil, and where « o( «.vo i& calculated according to the equation:
• the at least one polyester component is preferabl a eopolyester containing a metal sulfonate salt group.
• the metal sulfonate salt group is preferably a metal sulf isophthalate derived from a metal salt of 5-suI oisophthalie acid, its dimethyl ester or its glycol ester, it is further disclosed that the metal salt of S-suifoisophthalie acid, its dimethyl ester or its glycol ester may further comprise a metal, ion selected from the group consisting of Na Li '" , K Ztf 5 ", in ⁇ Co ⁇ and Ca ⁇ * It is further disclosed that the metal sulfonate salt group is preferably in a range selected, from the group consisting of 0.01 to 10.0 mole percent, 0,01 to 2.0 mole percent, 0.05 to .1.1 mole percent, 0.10 to 0.7-4 mole percent and 0.10 to 0,6 mole percent based, upon the total moles of acid
• the transition metal catalyst may be a compound containing at least one cobalt atom in a positive oxidation state.
• K is further disclosed that the transition metal catalyst may be a salt containing at least ' one cobalt atom in a positive oxidation state.
• the transition metal catalyst may be added to the com sition at a level in a range selected from the group of between 10 and 600 ppm, between 2.0 and 400 pprn and between 40 and 200 ppm of metal relative to the total amount of the polyester components and vegetable oil present in the composition.
• the vegetable oil is preferably selected from the group consisting of flax seed oil, linseed oil, evening primrose oil, borage oik sunflower oil, soybean oil, grapeseed oil, com oil, cotton seed oil, rice bran oil, canola oil and peanut oil.
• the composition may have a concentratio of the double allylk structures of the vegetable oil in the composition greater than 7.0 meq/fcg of all of the polyester components. It i further disclosed that the composition may have a concentration, of the double aliySie structures of the vegetable oil. in the composition greater than. 9,0 meq/fcg of all of the polyester components, it is further disclosed that the composition may have a concentration of the double atiyiic structures of the vegetable oil In the composition greater than 14.0 me /kg of all of the polyester components.
• the composition may further comprise a polyamide.
• the preferred polyamide is poly-metaxylylene adlpamide.
• the polyamide may be present in the composition at a level in a range selected from the gro up consisting of between 0.1 and. 0.9 % b weight of the total composition, 0.1 to 0,8 % by weight of the total composition* 0.1 to 0.7 % by weight of the total composition and 0.1 to 0.6 % by weight of the total composition.
• a preform having an ⁇ value of less than 20 Also disclosed herein is a preform having an, y value of less than 1.0. Also disclosed herein is a preform having an value of less than 5, Also disclosed herein is a biaxiatly oriented container manufactured from a preform.
• an article having a wall comprising a composition which may comprise at least one polyester component, a transition metal catalyst, and vegetable oil comprising at least one molecule having a double allyiic structure, wherein the at least one polyester component may comprise at least one acid unit and at least one dio.1 unit, the concentration of the double alivlic structures of the vegetable oil in the composition ma be greater than 5.0 meq/kg of all of the polyester components, and the wall may have a wall thickness less than 3.5 mm.
• the at least one polyester component may be a copolyester containing a metal sulfonate salt group.
• the metal sulfonate salt group may bo a metal suifbisophthalate derived from a metal salt of S-sulfoisophthalic acid, its dimethyl ester or its glycol ester, it is further disclosed that, the metal salt of S-siilfoisophthalic acid, its dimethyl ester or its glycol ester may comprise a metal ion selected from the group consisting of Na r , Li " , T , Zn *' , n ⁇ Co ⁇ and Ca" '" , It is further disclosed thai the metal sulfonate salt group is preferably In.
• the transition metal catalyst may be a compound containing at least one cobalt atom in a positive oxidation state * it is further disclosed that the transition metal catalyst is preferably a salt containing at least one cobalt atom in a positive oxidation state, it is further disclosed that the transition metal catalyst is preferably added to the composition at a level in a range selected from the group of between 10 and 600 ppm, between 20 and 400 ppm and between 40 atid 200 ppm of metal relati ve to the total amount of the polyester components and vegetable oil present in the composition.
• the vegetable oil is preferably selected from the group consisting of flax seed oil, linseed oil, evening primrose oil, borage oil sunflower oil* soybean oil, grapeseed oil, corn oil, cotton seed oil, rice bran oil, canoia oil and peanut oil.
• the composition may have a concentration of the double allylic structures of the vegetable oil in the composition greater than 7,0 meq/kg of all of the polyester components. It is further disclosed that the composition: may have a concentration of the double ally He structures of the vegetable oil in the composition greater than 9.0 meq kg of all of the polyester components. It is further disclosed that the compositio may have a concentration of the double allylic- structures of the vegetable oil in the composition greater than 14,0 meq/kg of all of the polyester components ,
• the composition further may comprise a polyamide.
• the preferred polyamide is poiy-metaxylylene adtpamlde.
• the polyamide may be present in the composition at a level in a range selected from the group consisting of between 0,1 and 0,9 % by weight, of the total composition, 0,1 to 0.8 % by weight of the total composition, 0,1 to 0,7 3 ⁇ 4 by weight of the total composition and 0,1 to 0.6 % by weight of the total composition.
• the article may have a wall thickness less than 3.0 mm. It is further disclosed thai the -article may also have a wall thickness less than 2,45 mm..
• the article is a film. It is further disclosed that the article is a sheet. It Is fcrtlier disclosed that the article is. a preform. Also disclosed herein is a biaxiali oriented container manu acture from a preform,
• Diaiiylic structures are found in, for instance, linoleie acid, which is a common component of several vegetable oils.
• Another type of double allylic structure Is a bis Diaiiylic having the general structure:
• Bis Diaiiylic structures are found in, for instance, hnoienic acid, which is a common component of several vegetable oils. What the inventors have found Is that the vegetable oil can be an. oxygen scavenger in. Its own right when the concentration, of vegetable oil in the composition is above a critical threshold, The critical threshold is considered to be the level at which the vegetable oil is n longer completely sohibilized in the polymer. Wi thout wishing to be bound by any theory, it Is believed that, if all of the vegetable oil Is solubilfoed in. the host polymer, there are no reactive sites available for scavenging oxygen. However, if the vegetable oil I added at a concentration such that not all of the vegetable oil is solubih3 ⁇ 4ed.
• the vegetable oil will form reactive domains in the composition which are evidenced by increased haze.
• This increased haze can be controlled by controlling the co and or ⁇ values for the composition as described herein, While the solubility of the vegetable oil in the- polymer will vary slightly depending on the type of vegetable oil used, in general the inventors have found that oxygen scavenging occurs when the vegetable oil is present In the composition at a level selected from the group consisting of greater than 0.6 % by weight relative to the total weight of the polyester components, the transition metal catalyst and the vegetable oil, greater than 0.5 % by weight relative to the total weight of the polyester components, the transition metal catalyst and the vegetable oil, greater than 0.4 % by weight relative to the total weight of the polyester components, the transition metal catalyst and the vegetable oil and greater than 03 % by weight relative to the total weight of the polyester components, the transition metal catalyst and the vegetable oil
• the composition results ' in a preform, container* sheet or film having active oxy gen scavenging characteristics when substantially void of a
• the miHiequivalents per kilogram (meq/kg) of double al!yiie structures is determined by -first calculating the mniole/kg of molecules containing mono Diallvlic structures and the mmole/kg of molecules containing bis DiailySie structures in the respective vegetable oil. For example, where the vegetable oil contains 15% by weight Iinoleic acid having a molecular weight of 280.45, the mmole/kg of mono
• Diallylie .structures in the vegetable oil is 534.85, (( ⁇ ⁇ ⁇ 3 ⁇ 4; 10,000 ⁇ 534-85), Where the vegetable oil also contains 54% by weight lindlenic acid having a molecular weight of 278.43* the mmole/kg of bis Diallylic structures in the vegetable oil is 1,939.45, ( ,,,, ⁇ x 10,000 ⁇
• meq/kg of double allylie structures in the vegetable, oil Is known this value can be used to calculate the miiiiequivalents per kilogram of polyester components In the final corn-position by dividing this number by the weight of the polyester components in the composition.
• the vegetable oil have a concentration of double al ly tic structures greater than 1 00 .eq/fcg, greater than I 500 meq/kg, greater than 2000 meq kg, or greater than..2300 m.eq/kg, where the concentration is a measure of the mifliequivalents rf the double allyiie structure relative to the weight of the vegetable oil.
• this discovery is- to a composition for containers comprising at least one polyester component which Is a copolyester containing a metal sulfonate salt group, a transition metal catalyst, and a vegetable oil comprising at least one molecule having a double .allyiie structure, wherein the copolyester containing a metal sulfonate salt group comprises at least one acid unit and at least one dial unit, the concentration of the double allyiie structures of the vegetable oil in the composition is greater than 5,0 meq/kg of ail of the polyester components, greater than 7,0 meq/kg of all of the polyester components, greater than 9.0 meq kg of all of the polyester components, or greater than 14.0 meq/kg of all of the polyester components.
• the composition may also contain poiyamide. Where a polyarokle is included it is preferred, thai the poiyamide is poly-me axylylene adipamide, Poiy-metaxyiylene adipamide is a partially aromatic- poiyamide sold commercially as MXD6 available from Mitsubishi Gas Chemieal Co. Where the poiyamide is present it is preferred that the poiyamide is present at level in a range selected from the group consisting of between 0.1 and 0.9 % by weight, of the total composition, 0.1 to 0.8 % by weight of the total composition, 0.1 to 0.7 % by weight of the total composition and 0.1 to 0,6 % by weight of the total composition. In one embodiment, the composition may be substantially void of a poiyanikle or entirely void of a poiyamide.
• the metal sulfonate salt group has bee .found t dramatically increase the amount of oxygen scavenging of the vegetable oik
• the Hunter L " reduction can be reduced by increasing the amount of cooling applied to the article, it has been found that when the cooling is increased, it is possible to produce a preform having a value, i3 ⁇ 4 of less than 260, less than 93, less than 24, less than 20, or less than 15 in an equation where l is a Hunter L measurement In me range of between 0 and. 100 excluding 0 and t is the thickness of the preform wall in am,
• L * is a Hunter L * measurement in the range of between 0 and 100 excluding 0 cuisine i is the thickness of the preform wall in mm
• the composition comprises a vegetable oil, and. where 3 ⁇ 4wo «tvo -is calculated according to the equation:
• the composition is the same as the composition used to calculate the value of t» w /vo > the preform comprises the same dimensions and. weight as the preform used, to calculate the value of ft ' 1 ⁇ 2/vo > a d the composition does not comprise a vegetable oil.
• the preform comprising vegetable oil When the preform comprising vegetable oil is made according to the teachings of this specification, it will, have a ⁇ value of less than 50, with less than 20 being more preferred, with less than .1.0 being even more preferred and less than 5 being the most preterred.
• the polyester component is a polyester formed by the reaction product of at least on dicarboxyiic acid or Its ester derivative and at least one diol.
• One useful polyester is a polyester with more than 85% of its acid units being derived from terephfhalie acid.
• polyester component i a copoiyesier containing a metal sulfonate salt group which can be prepared by polymerization procedures well-known in the art.
• the copolyester containing a metal sulfonate salt group may be prepared by melt phase polymerization involving the reaction of at least one diol unit with at least one dicarboxylio acid or its corresponding ester (the at least one acid unit) and a metal salt of S-si f isophthaiie acid or its corresponding ester.
• the copoiyesier containing a metal sulfonate salt group may be prepared, for example, b melt phase polymerization involvin the reaction of at least one diol with at least one dicarboxylie acid or its corresponding ester and a metai salt of S-sulfoisophthalie acid or its corresponding ester.
• Various copolymers resulting from use of multiple dio!s and dicarboxylie acids may also be used.
• Polymers containing repeating units of only one chemical composition are hom.opoly.mers. Polymers with two ot more chemically different repeat units i the same macromoiecule ate termed copolymers.
• copolymers include reacting one or more dlois with a diaeid or multiple cliaeids,. and are sometimes referred to as terpolymers.
• a polyethylene terephthalate copolymer comprised of ierepiithalie acid, isophthallc acid and the lithium salt of S-su!fbisophthalic acid is a copoiyesier.
• Suitable dicarboxylic acids include those comprising from about 4 to about 40 carbon atoms.
• Specific dicarboxylie acids include, but are not limited to, ierephtlialie acid, isophthalic acid, naphthalene 2, 6-dicarboxylic acid, cyclohexanediearboxyiie acid* eyciohexanedtacetic acid, dipheiiyl-4,4 , -dicaf boxy lie acid, I s 3 -plienylenedioxydi acetic acid, 1 ,2 ⁇ pheny lenedioxydiaeetic acid, 1,4-phenylenedioxydiacetic acid, succinic acid, gloiaric acid, adipk acid, azelaic acid, sebaeic acid, iuran ⁇ 2 !
• esters include, but are not limited to, phthalic esters and napMhalic dieslers.
• a useful polyester is a polyester with more than 85% o lis acid units being deri ved from terephthalic acid.
• These acids or esters may be reacted with an aliphatic diol preferably having from about 2 to about 24 carbon atoms, a eyeloaliphatie diol havin from about 7 to about 24 carbon atoms, an aromatic diol. having fro about 6 to about 24 carbon atoms, or a glycol ether having from 4 to 24 carbon atoms.
• Suitable diols and glycol ethers include,, but are not limited to, ethylene glycol, 1,4-butanediol, tximethylene glycol, 1 ,6-hexanedioi, 1,4-cyeiohexanedimethanol, diethylene glycol, resorcirsol, i ⁇ propanediol, neopbenthyl glycol, isosotbide, 2,2,4,4- tetramethyl- 1 ,3-cyclobutanedioi (TMCD) and hydroquinone,
• TMCD 2,2,4,4- tetramethyl- 1 ,3-cyclobutanedioi
• Polyfunetional comononiers can also be used, typicall in amounts of from about 0,0 f to about 3 mole percent, Suitable comononiers include, but are not limited to, trimellitic anhydride, trtmethylolpropane, pyromeliitic dianhydride (P DA), and pentaerytliritol. Polyester-forming polyacids or polyols can also be used. Blends of polyesters and eopoiyesters may also be useful in the present invention.
• di-ethyle e glycol is formed irs-situ in the manufacture of polyesters having ethylene glycol as their starting diol and that, about 2 to 3 percent of the total
• the composition may have 97 mole percent of its dioi units as ethylene glycol and 3 mole percent of its dioi units as di-ethylene glycol.
• the ester ification or polycondensaiion reaction of the carboxylic acids or their esters with the dioi.(s) typically takes place .i the presence of a catalyst.
• Suitable catalysts include, but afe not limited to, antimony oxide, antimony triacetate, antimony ethylene glycolate, organornagnesium, tin oxide, titanium aSkoxides, dibutyl tin diSaurate, and germanium oxide. These catalysts may be used in combination with zinc, m ng nese, or magnesium acetates or benzoates. Catalysts comprising antimony are preferred.
• the metal sulfonate salt group is preferably a metal sulfoisophihalate derived from a metal salt of S-sulfoisophthaSic acid its dimethyl ester or its glycol ester.
• the metal salt of 5- sulfoisop!hthalic acid comprises a metal ion selected from the group consisting of Na , ⁇ . ⁇ , K * t Zn 2" , Mn " Co " ⁇ Ca i+ and the like.
• the copolyester containin the .metal sulfonate salt group is made by eopoiymerixing the metal sulfonate into the polymer chain,
• One suitable copolyester containing a metal sulfonate salt group is a copolymer of polyethylene terephtbalate (PET) modified with a metal sulfoisoplithalaie derived from the di- ester or di-carboxy c acid of a metal sulfoisophihalate in the approximately 1:1 stoichiometric reaction of acids, or their di-esters, with ethylene glycol.
• PET polyethylene terephtbalate
• copolymers and terpoiymers also include crystallizable and non-crystal Sizable polyesters comprising a metal sulfotsophthalate in combination with isophthalic acid or its diester, 2,6 naphthaSate dicarboxySic acid or its diester, and/or oyclohexane dimethanol.
• the amount of metal sulfonate salt group in the polyester component is preferably in the range of about 0,01 to 10,0 mole percent based on the total acid units in ail of the polyester components of the composition, with an optimal, amount being in the range of about 0,0.1 to about..2.0 mole percent based on the total acid units in all of the polyester components of the composition* with the range of about 0.05 to about 1,1 mole percent based on the total acid units .
• ail of the polyester components of the composition being more optimal, and about 0,10 to about 0,74 mole percent based on the total acid units in all of the polyester components of the composit ion being even better yet, with the range of about 0,10 to about 0,6 mole percent based on the total acid units in ail of the polyester components of the composition being the most optimal range.
• the amount of metal sulfonate salt group in the composition is calculated
• One preferred metal su!foisophihaiate is derived from S-Hthiumsulfotsophthalic acid.
• the molecular structure of S-Iitliitm si exertophihahc acid is:
• the 5-liihiumsoifoisophtha!ie acid is a lithium sulfonate and comprises lithium suiioisophthalate.
• the lithium suiioisophthalate refers to the compound as it Is appears incorporated Into the polymer chain.
• This is also known as the repeating unit of 5-Hthiumsulfoisophthaiic acid * Lithium sulfoisophchalate therefore is the 5- HthtumsolfQisophtbalic acid less one water molecule, with one hydroxy! group removed from one of the carboxyl end groups and a hydrogen removed from the other carboxyl end group. This molecule is then attached to one or more monomers (Rj and ?) lit the polymer backbone.
• the metal sulfonate salt group in this case lithium su!fotsophihaiate, is the molecule between the two R groups.
• R could be the same monomer, in the case of PET, the R's are likely the same being the ethylene glycol moiety as reacted into the polymer chain.
• Typical levels of the metal sulfonate salt group In a polyester polymer range from 0.01 mole percent to 15 mole percent with respect to the total number of moles of the respective acid unit.
• a typical homopo!ymer polyester has 100 mole percent terephthalic acid units and 100 mote percent glycol units (ethylene glycol and di-ethylene glycol) *
• a polyester containing 5 mole percent of a metal salt of suifoisophthalic acid co-monomer would be derived from 95 moles of terephthalie acid., 5 moles of metal sulfonate (such as 5 itfiium$ulfotsophthalie acid) and 100 moles of ethylene glycol.
• a 2 mole percent isophthalate polymer would contain 93 moles terephthalie acid, 2 moles of isophthalic acid, 5 moles of metal sulfonate (such as 5-litfrium$ulibisopht1 ⁇ 2iie acid) and 100 moles ethylene glycol to make 100 moles of the polymer repeat unit
• Example* of copolyesters containing a metal sulfonate salt group employed in the present invention are those prepared b virtually any polyeondensation polymerization procedure,
• the traditional techniques can be divided into the ester, acid, and modified processes.
• the ester process* the dimethyl ester of the diearboxytic acid or acids is reacted with the dio! or diols in the presence of heat and the methanol removed yielding the bis-hydroxyethyt ester of the acids.
• the bis-hydroxyethyl ester is then polymerized in its liquid form by subjecting the material t vacuum and heat to remove the glycols and increase the molecular weight
• a typical process for the object polymer would start with these ratios: 98 moles of dimethyl terephtlialate, 2 moles of dimethyl lithium salt of sn exertophthalate and 220 moles of dio!., typically ethy lene glycol., Of the 220 moles of diot, 120 are excess which are removed during processing * it should be noted that it is possible to obtain the sulfonated co-monomer in either its bis ⁇ (hydraxyetliyi) or dimethyl ester form.
• the phrase copolymerked with at least X percent of a specific acid means that the compound is considered as part of the aeid. group of the polymer, such as terephthai c or isophthalic acid. It provides the reference to determine how many moles of the compound to use. The phrase does not mean that the compound must be added to the process as an acid.
• S-lithiumsulioisophthalic acid could be copolymerized into polyeth lene terephthalate as the acid, with two earboxylie end groups, the dimethyl ester of the catboxyiie acid, or the bishydroxy ester of the dimethyl ester or even, very low molecular weight oligomers of a glycol acid polymer where the acid units are at least in part, the sulfbisophthaiate salt
• copolymerized with'* means that the compound has been chemically reacted with the polymer, such as in the polymer chain or as a pendant group *
• a polyester copoiymerked with lithium sulfoisophthalate, or modified by copolvmerizing at least 0.01 mole percent S-iithiumsulfbisophihalic acid into the polyester means that the lithium siilfoisophthaSate is bonded to the polymer, including bound into the polymer chain, with at least one chemical bond.
• the phrases are indifferent to how the material is incorporated into the polymer.
• a polyester copoly.mer.ized with lithium, solfoisophthalate, or modified by copolymerizing at least 0.01 mole percent lithium snifoisophthalate into the polyester refers to a polyester containing the lithium suifoisaphthaiaie whether that lithium sulfoisoph ha e was incorporated, using but not limited to 5-hthitmisui.foisophthalie acid, lithium solfobenzoie acid, th dimethyl ester of 5- lithmmsulfolsophthatlc acid, the methyl ester of lithium suifobenzolc acid, the di-alcoho!
• lithium sidfossophtha!ate the lithium suliohydroxy benzene
• the lithium salt of hydroxy benzene sulfonic acid or oligomers or polymers containing the li thium, sulfoisophthalate.
• nd der vatives and “and I s derivatives* * refer to the various ftracttonalked forms of the metal sulfonate salt which can be copolymerized Into the polymer.
• lithium, suifblsophthalaie “and its derivatives” refers collectively and is not limited to 5- lithitsmsulfolsophthaSlc acid, the dimethyl este of S-iithluirrsuSfoisophihalic acid, the bis- hydroxyethyl ester of 5-lithiutnsu!fo ' isophfha!ic acid f the di-aleohol of lithium stdfoisophfhaSate, low molecular weight oligomers, and high I.V. polymers containing, lithium sidfossophtha!ate in the polymer chain.
• the starting materials are the diearboxyiic acids, with water being the primary by-product.
• the charge ratio In. a typical, acid process is 98 moles ierephihaiic acid, 2 moles of a metal salt of sulfoisophthalic acid (e.g. 5-iKhiumsulfoisophthalic acid - USIPA), and 120 moles of diols, typical ethylene glycol.
• the material is subjected to the same polymerization process conditions as the ester process.
• the modified processes are variations of either process: combining the intermediary product at certain steps.
• One example is to pre-po!ymerize the raw materials without the metal salt of sulfoisophthalic acid to a .low molecular weight
• the molecular weight of the low molecular weight polyester was typically in the range 0,096 to OJ03 di/g having a carboxyS end group number ranging from 586 to 1740 equivalents per 1,000,000 grams of polymer.
• the molecular weight could be easily varied without undue experimentation as it has been, for man years by those of ordinary skill in the art when optimizing the addition point for their additives.
• Another example of a variation is to use the acid process with just terephthalio acid, to produce its low molecular weight intermediate and the ester process used to produce the bis- hydroxy eth l ester of the homopolymer sulfonated polyester. These two Intermediates arc then combined and polymerized to a copolymer.
• Another variation is to add the finished modified polymer to the melt reactor and let the melt process depolymerise the modified polymer and then form a copolymer.
• the copoSyester of this invention may also contain small amounts of phosphorous compounds, such as phosphates. Also, small amounts of othe polymers such as po!yoiefins can be tolerated in the continuous matrix.
• the polymer is either made into a form .such as a film or part or stranded -and cut into .smaller chips, such as pellets.
• the polymer is usually then crystallized and subjected to a solid phase (solid state) polymerization (SSP) step to achieve the intrinsic viscosity necessary for the manufacture of certain articles such as bottles.
• SSP solid state polymerization
• the crystallization and lymerizati n can be performed in a tumbler dryer reactor in a batch- type system.
• the solid phase polymerization ca continue in the same tumble dryer where the polymer is subjected to high vacuum to extract the polymerization by-products.
• the crystal lizati n and polymerization can. be accomplished in a continuous solid state polymerization process whereby the polymer flows from one vessel to another after its predetermined treatment in each vessel.
• the crystallization conditions are relative to the polymer's crystallization and. sticking tendencies.
• preferable temperatures are from about iOO °C to about 235 C.
• the solid phase polymerization conditions are generaliy 10 X below the melt point of the polymer, in the ease of ndn-crystatlisable polyesters, the solid phase polymerization temperature is generally about 10 °C below temperature where the polymer begins sticking to itself.
• the solid phase polymerization may be carried out for a time sufficient to raise the intrinsic viscosity to the desired level* which will depend upon the application.
• the preferred intrinsic viscosity I.V.
• the time required to reach this L V from about 8 to about 21 hours.
• Vegetable oils of the present invention may be selected from the group consisting of flax seed oil, linseed oil, evening primrose oil, borage oil, sunflower oil, soybean oil, grapeseed oil, corn oil* cotton seed oil, rice bran oil, cano!a oil and peanut oil *
• the vegetable oil comprises at least one molecule having a double ai!yhe structure.
• Double allyiic structure is a mono DiaSlylic having the genera! structure
• Mono Diallylic structures are found in, for ' instance, linoleic acid, which is a common component of many vegetable oils.
• Another type of double al!ylic structure is a bis Diallylic having the general structure
• Bis Diallyli structures are found in, for instance, linolenic acid, which is also a common component of several vegetable oils.
• Linoleic acid has the general structure of:
• Flax seed oil is raw, cold pressed oil. derived from, the seed from the plant Linum usitatissimum. Flax, seed oil is a poly-unsaturated ester having a mixture of fatty acids, primarily In the form of triacySglycerides, with each triacylgiyceride comprised of three acids selected from the group consisting of triply saturated at ha-iinolenic acid, saturated acid palmitic acid, saturated acid stearic acid, monosaturated oleic acid, and doubly saturated linoleic acid.
• the poly-unsaturated ester of flax seed oil has the general structure of:
• Flax seed oil is well known for having trie alpha4i.no lenic acid as i s largest constituent Flax seed oil is available as the cold pressed oil (known simply as flax seed oil) or as a chemically treated and heated oil derived from the flax seed (known as Unseed oil).
• the cold pressed flax seed oil is preferred over the chemically treated and heated linseed oil as it is generally .regarded as safe for human consumption.
• Vegetable oil is used as an oxygen scavenger in the compositions disclosed herein.
• the vegetable oil is added at a level uch that the concentration of double allylic structures of the vegetable oil in the composition Is greater than 5.0 meq/kg of the total polyester components, greater than 7,0 meq kg of the total polyester components, greater than 9.0 meq kg of the total polyester components,, or greater than 14,0 meqkg of the polyester components.
• the vegetable oil can be added during the polymerization process of the copolyester containing a metal sulfonate salt group but is preferably added after the polymerization process, such as at the extruder or durin injection molding.
• oxygen scavenging may be assisted by the use of a transition metal catalyst.
• a transition metal catalyst Is compound containing at least one cobalt atom in a positive oxidation state.
• a more preferred transition metal catalyst is a salt containing at least one cobalt atom in a positive oxidation state-
• One preferred transition metal catalyst is a cobalt salt in which the cobalt forms at least a portion of the compound's cation.
• Preferred cobalt salts include cobalt chloride, cobalt " acetate, cobalt propionate, cobait steatate, cobalt octoate, cobalt neodecanoate, cobalt oleate, cobalt Hnoleate, cobalt salts of kannv acids, cobalt salts of short chained faftv acids, cobait salts of medium chained fatty acids, cobait salts of Song chained fatty acids, cobalt carbonate and combinations thereof.
• the preferred cobalt salt is an organic cobait salt with the inorganic cobait salts which can be solubifee in the polyester being less preferred.
• the cobalt atom of the cobalt compound may also exist in the anion of the compound, such as lithium cobaltate (LiCoQj) and potassium tris(oxalato)cobaltate( I).
• the cobaltate may also be formed in situ by the reaction of the cobalt atom in the presence of the polyesters carboxyiic acids in the presence of an alkali metal base.
• the cobait compound may also be a cobalt " complex such as cobalt glyeolate,
• the transition metal catalyst is preferably in a range of between 10 and 600 ppm of metal relative to the total amount of the polyester components and vegetable oil present In the composition with a level, in the range of between 20 and 400 ppm relative to the total amount " of the polyester components and vegetable oil present in the composition being more preferred and a level in the range of between. 40 and 200 ppm relative to the total amount of the polyester components and vegetable oil present in the composition being most preferred.
• the transition metal catalyst may be added during the polymerization process of the polyester component and/or the copolyester containing a metal sulfonate salt or it ma be added a the polymerizatio process, such as at the extruder or during injection molding.
• the polyester may be polymerized in the presence of a phosphorous compound, such as poiyphosphoric acid, phosphoric aetd » or trieihyi phosphate, for example.
• a phosphorous compound such as poiyphosphoric acid, phosphoric aetd » or trieihyi phosphate, for example.
• the components of the composition are often melt blended in an injection molding extruder to make a film, sheet or preform.
• the preform can then, be biaxiai.ly stretched, such by reheat, blow molding, to form a biaxiai.ly oriented container.
• the rnilkiness can he reduced b adding additional, cooling after injection molding. Additional cooling can he achieved by reducing the injection molding- temperature, decreasing the temperature of the injection molding cooling liquid, increasing the time that the composition is held in the mold, decreasing the wall thickness of the article or any combination thereof
• additional cooling is achieved by decreasing the wall thickness of the article, it is preferred that the wall thickness be less than 3.5 mm, with a wall thickness less than 3.0 mm being more preferred and a wall thickness less than 2 * 45 mm bein even more preferred.
• the val ue of is less than 260 with an to value less than 93 being more preferred, -an w value less than 24 being even more preferred, an to value less than 20 being still .more preferred and m ⁇ > value less than 5 being most preferred.
• the increase in mHkiness can also be assessed by determining the value of ⁇ in an equation
• L is a Hunter L measurement in the range of between 0 and 100 excluding 0, t is the thickness of the preform wail in mm, and the composition comprises a vegetable oil, and where ®w3 ⁇ 4uivo * s calculated according to the equati
• the composition is the same as the composition used, to calculate the value of a yo? ' the preform comprises the same dimensions and weight as ' the preform used to calculate the value of evvo, and the composition does not comprise a vegetable oil
• the value of ⁇ is less than 50 with a ⁇ value less than 20 being more preferred, a y value less than 10 being even more preferred and a ⁇ value less than 5 being most preferred.
• compositions disclosed herein may include additional additives including colorants, pigments, fillers, acid -scavengers, processing aids, coupling, agents, lubricants, stearates, blowing agents, poiyhydrie alcohols, nucleating agents, antioxidants, antistatic agents, ⁇ V absorbers, slip agetns, and-fbgging agents, anti ⁇ condensation agents, suspension stabilizers, anti-blocking agents, waxes and mixtures thereof.
• additives are added at levels not inconsistent with the end use to make a commercially acceptable container. Generally, these additives are added at a level less than 5 % by weight of the composition..
• the ability of a vegetable oil to scavenge oxygen was tested according to the following procedures,
• the PET resins PETS, PET.2, SiPAL, SIPA2
• PET.2, SiPAL, SIPA2 were dried (177 °C, .5 hours, desiccated air) using, a ConAif D175 Desiccant Carousel, then cooled and held at 135 in the dryer until injection molding.
• the experimental compositions for injection molding were prepared by mixing the various PET/S1PA resins and vegetable oils together in a metal can.
• Compositions comprising at least one polyester component, a transition, metal catalyst -and a vegetable oil were blended in an Arburg 420C injection molding extruder and molded into preforms.
• compositions were injection molded into either 28 gram preforms having a 4 mm wall thickness or .18 gram preforms having a 2,44 M wall thickness as indicated in the tables below. These preforms were then blown into 500 ml. bottles. Unless otherwise indicated, the materials used in the experimental compositions include;
• Poliprotect S resin comprising 033 mole % LiSIPA and containing 138
• the 28g preforms were Injection molded using the following injection molding conditions:
• compositions comprising the components listed i Table 1. below were tested. In each run, the specific PET and SIPA components were blended to achieve the reported final SiPA mole %, Runs 1 through 3 utilized PETl resin. Runs 4 through 6 utilized PET.2 resin in combination with SlPAl resin.
• the SIPA mole % reported Irs Table I Is the measure of the moles of metai sulfonate salt group based upon the total moles of acid units in all of the polyester components in the composition,.
• the amount of cobalt reported in Table 1 is the measure of ppm cobal t from cobalt neodecanoate relative to the total amoun t of the pol yester components and the vegetable oil present in the composition.
• the weight % of FSOl reported in Table 1 is the measure of the weight of flax seed oil relative to the total weight of the polyester components, the transition metai catalyst (cobalt salt) and the flax seed oil.
• the double atlylic concentration reported in Table 1 is the milliequivendings of the double al lytic structures in FSOl relative to the total weight of the polyester components (PE and. SIPA) in kilograms.
• Model 6000 to ensure equilibration between, the oxygen dissolved: in the liquid and the oxygen in the bottle headspaee.
• the fiber optic cable is attached to the top of the gas-tight plastic bottle insert.
• the meter reads the sensor dot and calculates the dissolved 0; ⁇ concentration while the bottle is gently shaken while lying on its side.
• the weight % of the vegetable oil reported, in Table 3 is the measure of the weight o.f vegetable oil relative to the total weight, of the polyester components, the transition metal catalyst (cobalt salt) and the vegetable oil.
• the double ally!ie concentration reported in Table 3 is the milliequivalents of the double aliylic structures in the vegetable oil relative to the total weight of the polyester components (PET and SIPA) in
• each vegetable oil tested will not scavenge oxygen at a lower concentration in the composition (Runs 7, 10, 1.3 and 16). However, when, added at a higher concentration. (Runs 8, 9, 1 !,. 12, 14, .1.5, 17 and I S) the vegetable oil will scavenge oxygen.
• compositions comprising at least one polyester component, a transition, metal catalyst and a vegetable oil were blended in an injection molding extruder and molded into preforms. Each preform was tested for color and haze using a HunterLab ColorQuest XE Spectrophotometer. Each preform was measured 4 times at 90° intervals in an immobilization j ig> and the average measurement was recorded. As the preform is hollow tube, the color find .haze values are the values measured through the entire pre.tb.wn. (I.e. two sidewalk).
• the composition is the same as the composition used to calculate the value of co w vo > the preform comprises the same dimensions and weight as the preform used, to calculate the value of e w vo > and the composition does not comprise a vegetable oil.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Health & Medical Sciences (AREA)
• Engineering & Computer Science (AREA)
• Manufacturing & Machinery (AREA)
• Mechanical Engineering (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Materials Engineering (AREA)
• Analytical Chemistry (AREA)
• Food Science & Technology (AREA)
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• Compositions Of Macromolecular Compounds (AREA)
• Polyesters Or Polycarbonates (AREA)
• Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
• Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
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